CN117106391A - Polyacrylate pressure-sensitive adhesive and preparation method and application thereof - Google Patents
Polyacrylate pressure-sensitive adhesive and preparation method and application thereof Download PDFInfo
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- CN117106391A CN117106391A CN202311128566.8A CN202311128566A CN117106391A CN 117106391 A CN117106391 A CN 117106391A CN 202311128566 A CN202311128566 A CN 202311128566A CN 117106391 A CN117106391 A CN 117106391A
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- sensitive adhesive
- polyacrylate pressure
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 90
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 62
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002904 solvent Substances 0.000 claims abstract description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003999 initiator Substances 0.000 claims abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012046 mixed solvent Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 239000003292 glue Substances 0.000 claims description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- 239000013557 residual solvent Substances 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 21
- 239000007787 solid Substances 0.000 abstract description 14
- 238000009826 distribution Methods 0.000 abstract description 7
- 239000002253 acid Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 12
- 150000001408 amides Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
The invention discloses a polyacrylate pressure-sensitive adhesive and a preparation method and application thereof, wherein the polyacrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 3-7 parts of hard monomer, 30-55 parts of soft monomer, 0.1-3.7 parts of functional monomer, 0.03-0.12 part of regulator, 0.1-0.5 part of initiator and 35-40 parts of solvent; the functional monomer is acrylic acid and acrylic acid amide with the mass ratio of 1-4:4-1; the solvent is a mixed solvent of ethyl acetate and toluene with the mass ratio of 2-4:4-6 or a mixed solvent of ethyl acetate and butanone with the mass ratio of 2-4:4-6; through limiting the types and proportions of the functional monomer and the solvent in the raw materials, the maximum molecular weight of the obtained polymer is obviously reduced, and the molecular weight distribution width is obviously reduced, so that the polyacrylate pressure-sensitive adhesive with high solid content has low acid value and excellent mechanical property, and simultaneously has lower viscosity, is more beneficial to coating during use and is beneficial to large-scale popularization and application of the polyacrylate pressure-sensitive adhesive with high solid content.
Description
Technical Field
The invention relates to the field of hyposensitive glue, mainly relates to the field of polyacrylate pressure sensitive glue, and in particular relates to a polyacrylate pressure sensitive adhesive with high solid content and low viscosity, and a preparation method and application thereof.
Background
The pressure sensitive adhesive is called as pressure sensitive adhesive, and is an important branch in the adhesive field. Because of its dry and permanent tack, it is commonly known as self-adhesive. It features easy adhesion, easy removal, no damage, and no drying in a long period. In recent years, with the expansion of the demand for various packages, office supplies, labels and the like, the demand for pressure-sensitive adhesives is increasing. The pressure sensitive adhesive is convenient to use and wide in application, so that the development is very rapid, and the growth speed in recent years at home and abroad is over 10%. The polyacrylate pressure-sensitive adhesive can be prepared into pressure-sensitive adhesives meeting various performance requirements by copolymerization and crosslinking, and generally has good pressure-sensitive adhesive performance without using additives such as tackifying resin, softening agent, anti-aging agent and the like, so that the formula is simple and easy to synthesize. The pressure-sensitive adhesive has the advantages of low toxicity, wide bonding surface, good weather resistance and the like, so the pressure-sensitive adhesive has very rapid development in the last 20 years, has replaced the dominant position of the natural rubber pressure-sensitive adhesive, and is widely applied to the industrial and civil fields.
Along with the enhancement of environmental protection consciousness and increasingly strict environmental protection laws, energy conservation and emission reduction work is gradually paid attention to all countries in the world. The traditional acrylic adhesive adopts a low-solid-content mode composite adhesive, wherein about 70% of the adhesive is a solvent, so that the coating amount is large, the production efficiency is low, a large amount of Volatile Organic Compounds (VOC) are discharged in the use process, the environment is polluted, and potential safety hazards are brought. Environmentally friendly adhesives such as high solids (not less than 50% solids) are increasingly replacing traditional adhesives, which meet the requirements of the age. The high-solid-content pressure-sensitive adhesive has the advantages of high drying film forming speed, greatly reduced transportation and storage cost, small environmental pollution and the like, so that the high-solid-content adhesive has wider development and application prospects. However, increasing the solids content leads to a sharp increase in viscosity and even to gelling. In order to ensure that the adhesive system is homogeneous in the polymerization reaction process, the selected solvent has good solubility for the initiator or the catalyst, the monomer and the polymer, so that the viscosity is reduced, the gel effect is slowed down, the polymerization reaction heat is led out, a mixed solvent can be used if necessary, but the high-solubility solvent is directly used, the mechanical property of the adhesive is influenced, and the application range of the product is limited.
Disclosure of Invention
The invention aims to solve the problems of high viscosity and difficult coating of the existing high-solid-content polyacrylate pressure-sensitive adhesive, and provides a polyacrylate pressure-sensitive adhesive, a preparation method and application thereof.
In order to achieve the aim of the invention, the invention provides a polyacrylate pressure-sensitive adhesive which comprises the following raw materials in parts by weight: 3-7 parts of hard monomer, 30-55 parts of soft monomer, 0.1-3.7 parts of functional monomer, 0.03-0.12 part of regulator, 0.1-0.5 part of initiator and 35-40 parts of solvent; the functional monomer is acrylic acid and acrylic acid amide with the mass ratio of 1-4:4-1; the solvent is a mixed solvent of ethyl acetate (ETAC) and Toluene (TOL) with the mass ratio of 2-4:4-6 or a mixed solvent of ethyl acetate (ETAC) and butanone (MEK) with the mass ratio of 2-4:4-6.
According to the polyacrylate pressure-sensitive adhesive, the molecular weight of a polymer is influenced by utilizing a functional monomer, so that the temperature resistance, the stripping force and the initial viscosity of a glue layer are influenced, the initiator is decomposed by the induction of a solvent, and the chain radical has a chain transfer reaction on the solvent, so that the polymerization rate and the molecular weight are influenced; through limiting the types and proportions of the functional monomer and the solvent in the raw materials, the maximum molecular weight of the obtained polymer is obviously reduced, and the molecular weight distribution width is obviously reduced, so that the polyacrylate pressure-sensitive adhesive with high solid content has low acid value and excellent mechanical property, and simultaneously has lower viscosity, is more beneficial to coating during use and is beneficial to large-scale popularization and application of the polyacrylate pressure-sensitive adhesive with high solid content.
Wherein, the hard monomer is a homopolymer capable of generating higher glass transition temperature (Tg), and can be copolymerized with the soft monomer to generate better cohesion, thus having obvious improvement effect on the adhesive strength of the polymer; preferably, the hard monomer is at least one of Methyl Acrylate (MA), vinyl Acetate (VAC), and isobornyl methacrylate.
Wherein, the main function of the soft monomer is to make the polymer generate lower Tg and have better initial adhesion property, thereby endowing the pressure-sensitive adhesive with better anchoring property; preferably, the soft monomer is at least one of n-butyl acrylate (n-BA), ethyl Acrylate (EA) and isooctyl acrylate (2-EHA).
The functional monomer mainly plays a role in influencing the molecular weight of the polymer, so as to influence the temperature resistance, the stripping force and the initial viscosity of the adhesive layer; preferably, the functional monomers are Acrylic Acid (AA) and acrylic acid Amide (AM) in a mass ratio of 2:3.
Wherein, the regulator is also called a molecular weight regulator, has good chain transfer capability, and the molecular weight of the polymer can be controlled by the dosage; preferably, the regulator is dodecyl mercaptan.
Wherein, the initiator can initiate the polymerization reaction of the monomer, and can control the speed and the molecular weight of the polymerization reaction; preferably, the initiator is at least one of dibenzoyl peroxide (BPO) and Azobisisobutyronitrile (AIBN).
Wherein the solvent has an induced decomposition effect on the initiator, and the chain radical has a chain transfer reaction on the solvent, which can affect the polymerization rate and molecular weight; preferably, the solvent is a mixed solvent of ethyl acetate and MEK with a mass ratio of 3:5; the preferable mixed solvent has a synergistic effect, can ensure that a polymerization system is homogeneous in the reaction process, and is favorable for leading out the polymerization reaction heat, so that the gel effect of a polymer can be slowed down, and the viscosity of the polymer is obviously reduced.
In order to achieve the aim of the invention, the invention further provides a preparation method of the polyacrylate pressure-sensitive adhesive, which comprises the following steps:
(1) Mixing 40-60% by weight of hard monomer, 40-60% by weight of soft monomer, 40-60% by weight of functional monomer, 40-60% by weight of solvent and 100% by weight of regulator in the polyacrylate pressure sensitive adhesive raw material to obtain a first mixed solution;
(2) Heating the first mixed solution to 73-75 ℃ in a protective atmosphere, and then adding 40-50% by weight of initiator to perform a first prepolymerization reaction;
(3) After the first prepolymerization reaction is carried out for 50-70min, adding all the rest hard monomers, soft monomers and functional monomers and 10-20 weight percent of initiator to carry out the second prepolymerization reaction;
(4) After the second prepolymerization reaction is carried out for 70-90min, heating to 93-95 ℃, adding all the rest initiator, and carrying out polymerization reaction for 2-4h;
(5) And after the polymerization reaction is completed, adding all the residual solvents, and uniformly mixing to obtain the polyacrylate pressure-sensitive adhesive.
According to the preparation method of the polyacrylate pressure-sensitive adhesive, through the mode of adding raw materials in batches and carrying out a prepolymerization reaction, the maximum molecular weight of a polymer is effectively reduced, and the molecular weight distribution range of the polymer is reduced, so that the obtained polyacrylate pressure-sensitive adhesive with high solid content has excellent adhesiveness and lower viscosity, is more suitable for coating in application, and is simple and reliable, good in operability, low in technical difficulty and suitable for large-scale and industrial production of the polyacrylate pressure-sensitive adhesive.
Preferably, the protective atmosphere in the step (2) is a nitrogen atmosphere.
Preferably, in the step (3), the hard monomer, the soft monomer and the functional monomer are mixed uniformly and then added into the reaction solution; the preferable adding mode can better ensure the uniformity of the polymerization reaction, and the obtained polymer has smaller molecular weight, narrower molecular weight distribution range and smaller viscosity.
Wherein, preferably, in the step (3), the initiator is added into the reaction liquid for at least 2 times, and the interval time is the same each time; the preferable adding mode can better ensure the uniformity of the polymerization reaction, and the obtained polymer has smaller molecular weight, narrower molecular weight distribution range and smaller viscosity.
In order to achieve the aim of the invention, the invention further provides an application of the polyacrylate pressure-sensitive adhesive tape in preparing pressure-sensitive adhesive tapes.
Wherein, preferably, the pressure-sensitive adhesive tape comprises a PET substrate layer, a release layer and a glue layer arranged between the PET substrate layer and the release layer; the glue layer is formed by coating the mixed glue solution on a PET substrate layer and drying; the mixed glue solution is prepared by mixing polyacrylate pressure-sensitive adhesive, a curing agent and a diluent.
Wherein, in the mixed glue solution, the ratio of polyacrylate pressure-sensitive adhesive is preferably 70-80%, the ratio of curing agent is preferably 0.6-1.2%, and the balance is diluent; the diluent is at least one of ethyl acetate, toluene and butanone; the curing agent is isocyanate curing agent.
Wherein, preferably, the thickness of the glue layer is more than 30 μm.
Wherein, preferably, the adhesive layer is prepared at a drying temperature of not more than 120 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. the polyacrylate pressure-sensitive adhesive provided by the invention has the advantages that the maximum molecular weight of the obtained polymer is obviously reduced and the molecular weight distribution width is obviously reduced by limiting the types and the proportions of the functional monomers and the solvents in the raw materials, so that the polyacrylate pressure-sensitive adhesive with high solid content is ensured to have low acid value and excellent mechanical property and also has lower viscosity.
2. According to the preparation method of the polyacrylate pressure-sensitive adhesive, the raw materials are added in a mode of carrying out a polymerization reaction in a divided mode, so that the maximum molecular weight of a polymer is effectively reduced, and the molecular weight distribution range of the polymer is narrowed, and the obtained polyacrylate pressure-sensitive adhesive with high solid content has excellent adhesiveness and lower viscosity.
3. The preparation method of the polyacrylate pressure-sensitive adhesive is simple and reliable, has good operability and low technical difficulty, and is suitable for large-scale and industrialized production of the polyacrylate pressure-sensitive adhesive.
4. The application of the polyacrylate pressure-sensitive adhesive tape in the preparation of the pressure-sensitive adhesive tape ensures low VOC emission and good performance of the pressure-sensitive adhesive tape, and is suitable for large-scale popularization and application.
Detailed Description
The present invention will be described in further detail with reference to test examples and specific embodiments. It should not be construed that the scope of the above subject matter of the present invention is limited to the following embodiments, and all techniques realized based on the present invention are within the scope of the present invention.
Example 1
The polyacrylate pressure-sensitive adhesive is prepared from the following raw materials in parts by weight: VAC 4 parts, soft monomer 40 parts (25 parts n-BA, 15 parts 2-EHA), functional monomer 3.0 parts (AA: am=1:4), dodecyl mercaptan 0.12 parts, initiator BPO 0.4 parts, solvent 40 parts (ETAC: tol=3:5).
The preparation method comprises the following specific steps:
(1) Mixing 50 weight percent of hard monomer, 50 weight percent of soft monomer, 50 weight percent of functional monomer, 50 weight percent of solvent and 100 weight percent of regulator in the polyacrylate pressure sensitive adhesive raw material to obtain a first mixed solution;
(2) Heating the first mixed solution to 74 ℃ in a protective atmosphere, and then adding 50 weight percent of initiator to perform a first prepolymerization reaction;
(3) After the first prepolymerization reaction is carried out for 60min, adding all the rest hard monomers, soft monomers and functional monomers and 10 weight percent of initiator to carry out a second prepolymerization reaction;
(4) After the second prepolymerization reaction for 80min, heating to 94 ℃, adding all the rest initiator, and carrying out polymerization reaction for 3h;
(5) And after the polymerization reaction is completed, adding all the residual solvents, and uniformly mixing to obtain the polyacrylate pressure-sensitive adhesive.
Example 2
Polyacrylate pressure-sensitive adhesive: the preparation method is the same as in example 1, except that the AA to AM ratio is changed to 2:3.
Example 3
Polyacrylate pressure-sensitive adhesive: the preparation method is the same as in example 1, except that the AA to AM ratio is changed to 3:2.
Example 4
Polyacrylate pressure-sensitive adhesive: the preparation method is the same as in example 1, except that the AA to AM ratio is changed to 4:1.
Example 5
Polyacrylate pressure-sensitive adhesive: the preparation was the same as in example 1, except that dodecylmercaptan was reduced to 0.09 parts.
Example 6
Polyacrylate pressure-sensitive adhesive: the preparation was the same as in example 1, except that dodecylmercaptan was reduced to 0.06 parts
Example 7
Polyacrylate pressure-sensitive adhesive: the preparation was the same as in example 1, except that dodecylmercaptan was reduced to 0.03 parts
Example 8
Polyacrylate pressure-sensitive adhesive: the preparation was the same as in example 1, with TOL replaced with MEK.
Example 9:
polyacrylate pressure-sensitive adhesive: the preparation method was the same as in example 5, except that ETAC/TOL was changed to 2:4.
Example 10:
polyacrylate pressure-sensitive adhesive: the preparation method was the same as in example 5, except that ETAC/TOL was changed to 1:1.
Comparative example 1:
polyacrylate pressure-sensitive adhesive: the preparation method is the same as in example 1, except that the AA to AM ratio is changed to 5:0.
Comparative example 2:
polyacrylate pressure-sensitive adhesive: the preparation method is the same as in example 1, except that the AA to AM ratio is changed to 0:5.
Comparative example 3:
polyacrylate pressure-sensitive adhesive: the preparation was the same as in example 1, except that only ETAC was used as solvent.
Comparative example 4:
polyacrylate pressure-sensitive adhesive: the formulation was the same as in example 1, except for the preparation method (one-time addition of the polymerized monomer);
the specific method comprises the following steps:
(1) Mixing hard monomers, soft monomers, functional monomers, solvents and regulators in the polyacrylate pressure-sensitive adhesive raw materials to obtain a first mixed solution;
(2) Heating the first mixed solution to 74 ℃ in a protective atmosphere, and then adding 50 weight percent of initiator to perform a first prepolymerization reaction;
(3) After 60min of the first prepolymerization, adding 10 weight percent of initiator to perform a second prepolymerization;
(4) After the second prepolymerization reaction for 80min, heating to 94 ℃, adding all the rest initiator, and carrying out polymerization reaction for 3h;
(5) And after the polymerization reaction is completed, obtaining the polyacrylate pressure-sensitive adhesive.
Comparative example 5:
polyacrylate pressure-sensitive adhesive: the formulation was the same as in example 1, except for the preparation method (initiator added in one portion);
the specific method comprises the following steps:
(1) Mixing 50 weight percent of hard monomer, 50 weight percent of soft monomer, 50 weight percent of functional monomer, 50 weight percent of solvent and 100 weight percent of regulator in the polyacrylate pressure sensitive adhesive raw material to obtain a first mixed solution;
(2) Heating the first mixed solution to 74 ℃ in a protective atmosphere, and then adding all the initiator to perform a first prepolymerization reaction;
(3) After the first prepolymerization reaction is carried out for 60min, adding all the rest hard monomers, soft monomers and functional monomers for a second prepolymerization reaction;
(4) After the second prepolymerization reaction is carried out for 80min, the temperature is raised to 94 ℃, and the reaction is carried out for 3h;
(5) And after the polymerization reaction is completed, adding all the residual solvents, and uniformly mixing to obtain the polyacrylate pressure-sensitive adhesive.
Experimental example:
the polyacrylate pressure-sensitive adhesives prepared in examples 1 to 7 and comparative examples 1 to 5 were prepared according to the following formulation: the polyacrylate pressure-sensitive adhesive accounts for 80 percent, and the isocyanate curing agent accounts for 1.0 percent and the toluene 19 percent are mixed to prepare mixed glue solution; and (3) coating the mixed glue solution on a PET film layer with the thickness of 25 mu m, drying for 8 minutes at the temperature of 110 ℃ to obtain a glue layer with the thickness of 30 mu m, and finally covering a release film with the thickness of 36 mu m on the surface of the glue layer to obtain the pressure-sensitive adhesive tape.
The polyacrylate pressure-sensitive adhesives in examples 1 to 7 and comparative examples 1 to 5 described above and the pressure-sensitive tapes prepared accordingly were tested for their properties, with the following test criteria,
solid content: GB/T2793-1995;
viscosity: GB/T21059-2007;
acid value:；
primary adhesion:；
glue layer thickness: GB/T7125-1999;
180 ° peel force: GB/T2792-1998;
holding viscosity: GB/T4851-1998;
the detection results are as follows:
| sequence number | Solid content (%) | Viscosity (mPas) | Acid value (mg KOH/g) | Glue layer thickness (mum) | Primary tack (#) | 180 DEG peel force (gf/25 mm) | Hold viscosity (mm) (80 ℃ C., 72 h) |
| Example 1 | 61.2 | 9812 | 10.2 | 25 | 10 | 1659 | 0 |
| Example 2 | 62.5 | 10257 | 19.5 | 25 | 12 | 1823 | 0 |
| Example 3 | 61.7 | 9220 | 31.3 | 25 | 12 | 1897 | 0 |
| Example 4 | 62.8 | 11217 | 40.8 | 25 | 13 | 1772 | 0 |
| Example 5 | 62.7 | 14217 | 18.9 | 25 | 14 | 2086 | 0 |
| Example 6 | 60.1 | 17200 | 19.1 | 25 | 14 | 2260 | 0 |
| Example 7 | 61.1 | 20234 | 20.0 | 25 | 16 | 2584 | 0 |
| Example 8 | 61.3 | 12293 | 19.8 | 25 | 18 | 2468 | 0 |
| Example 9 | 60.9 | 17232 | 19.2 | 25 | 13 | 2106 | 0 |
| Example 10 | 62.9 | 13189 | 19.5 | 25 | 14 | 2198 | 0 |
| Comparative example 1 | 62.7 | 21950 | 51.2 | 25 | 7 | 1497 | 0 |
| Comparative example 2 | 62.5 | 20355 | 1.3 | 25 | 3 | 1359 | 0 |
| Comparative example 3 | 60.8 | 117450 | 19.7 | 25 | 4 | 1099 | 0 |
| Comparative example 4 | 61.3 | 35560 | 10.2 | 25 | 5 | 1113 | 0 |
| Comparative example 5 | 60.8 | 41329 | 10.5 | 25 | 4 | 964 | 0 |
Analysis of experimental results: the experimental results in the analysis table show that the polyacrylate pressure-sensitive adhesive prepared in the embodiment of the invention has the solid content of 60.1-62.9%, the viscosity of 9220-20234 mPa.s, the 180 DEG peeling force of 1659-2584gf/25mm and the holding viscosity of 0 mm at 80 ℃ for 72 hours. The polyacrylate pressure sensitive adhesive of example 8 preferably has an initial tack (18 #). Specific: according to examples 1-4, the polyacrylate pressure sensitive adhesive performs better with tape at an AA to AM ratio of 2:3, indicating that at this ratio, AA and AM have a good synergy, resulting in better cohesion of the polyacrylate pressure sensitive adhesive and, relatively, lower acid number, less damage to the metal substrate. According to examples 4-7, the amount of dodecylmercaptan used was reduced, the sulfur content in the polymer was reduced, the environmental protection was facilitated, and the tape performance was improved. The difference between examples 8-10 and comparative example 3 caused by the selection of solvents, ETAC alone, too much viscosity of the polymer, and the selection of ETAC mixed with MEK or TOL, better dissolution performance, and the ratio of solvents also affects the viscosity. The preparation method of example 1 and comparative examples 4-5 also greatly affect the performance of the adhesive, and the addition of the adhesive in batches leads to more uniform molecular weight and better dispersibility. The overall monomer ratio, the dosage of dodecyl mercaptan and the choice of solvent can influence the viscosity of the adhesive, wherein the molecular weight of the polymer is reduced as the initiator is increased; chain termination is accelerated by increasing the amount of dodecyl mercaptan; the choice of solvent also has an effect on the degree of polymerization of the polymer, and different solvent chain transfer constants may deactivate the transfer of initiator radicals to the solvent, terminating chain growth. In conclusion, the polyacrylate pressure-sensitive adhesive disclosed by the invention not only can ensure low VOC emission, but also can ensure good performance of the pressure-sensitive adhesive tape, and is low in viscosity and easy to coat.
Claims (10)
1. The polyacrylate pressure-sensitive adhesive is characterized by comprising the following raw materials in parts by weight: 3-7 parts of hard monomer, 30-55 parts of soft monomer, 0.1-3.7 parts of functional monomer, 0.03-0.12 part of regulator, 0.1-0.5 part of initiator and 35-40 parts of solvent; the functional monomer is acrylic acid and acrylic acid amide with the mass ratio of 1-4:4-1; the solvent is a mixed solvent of ethyl acetate and toluene with the mass ratio of 2-4:4-6 or a mixed solvent of ethyl acetate and butanone with the mass ratio of 2-4:4-6.
2. The polyacrylate pressure sensitive adhesive of claim 1, wherein the hard monomer is at least one of methyl acrylate, vinyl acetate, isobornyl methacrylate.
3. The polyacrylate pressure sensitive adhesive of claim 1, wherein the soft monomer is at least one of n-butyl acrylate, ethyl acrylate, isooctyl acrylate.
4. The polyacrylate pressure sensitive adhesive of claim 1, wherein the functional monomers are acrylic acid and acrylic acid amide in a mass ratio of 2:3.
5. The polyacrylate pressure sensitive adhesive of claim 1, wherein the regulator is dodecyl mercaptan.
6. The polyacrylate pressure sensitive adhesive of claim 1, wherein the initiator is at least one of dibenzoyl peroxide, azobisisobutyronitrile.
7. The polyacrylate pressure sensitive adhesive according to claim 1, wherein the solvent is a mixed solvent of ethyl acetate and MEK in a mass ratio of 3:5.
8. A method for preparing the polyacrylate pressure sensitive adhesive according to any one of claims 1 to 7, comprising the steps of:
(1) Mixing 40-60% by weight of hard monomer, 40-60% by weight of soft monomer, 40-60% by weight of functional monomer, 40-60% by weight of solvent and 100% by weight of regulator in the polyacrylate pressure sensitive adhesive raw material to obtain a first mixed solution;
(2) Heating the first mixed solution to 73-75 ℃ in a protective atmosphere, and then adding 40-50% by weight of initiator to perform a first prepolymerization reaction;
(3) After the first prepolymerization reaction is carried out for 50-70min, adding all the rest hard monomers, soft monomers and functional monomers and 10-20 weight percent of initiator to carry out the second prepolymerization reaction;
(4) After the second prepolymerization reaction is carried out for 70-90min, heating to 93-95 ℃, adding all the rest initiator, and carrying out polymerization reaction for 2-4h;
(5) And after the polymerization reaction is completed, adding all the residual solvents, and uniformly mixing to obtain the polyacrylate pressure-sensitive adhesive.
9. Use of a polyacrylate pressure sensitive adhesive according to any one of claims 1 to 7 for the preparation of pressure sensitive adhesive tapes.
10. The use according to claim 9, wherein the pressure sensitive adhesive tape comprises a PET substrate layer, a release layer and a glue layer disposed between the PET substrate layer and the release layer; the glue layer is formed by coating the mixed glue solution on a PET substrate layer and drying; the mixed glue solution is prepared by mixing polyacrylate pressure-sensitive adhesive, a curing agent and a diluent.
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